Efficient transition path sampling for systems with multiple reaction pathways
A new algorithm is developed for sampling transition paths and computing reaction rates. To illustrate the use of this method, we study a two-dimensional system that has two reaction pathways: one pathway is straight with a relatively high barrier and the other is roundabout with a lower barrier. Th...
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| Veröffentlicht in: | The Journal of chemical physics 2005-09, Vol.123 (9), p.94104-94104 |
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| container_title | The Journal of chemical physics |
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| creator | Chen, L Y Nash, P L Horing, N J M |
| description | A new algorithm is developed for sampling transition paths and computing reaction rates. To illustrate the use of this method, we study a two-dimensional system that has two reaction pathways: one pathway is straight with a relatively high barrier and the other is roundabout with a lower barrier. The transition rate and the ratio between the numbers of the straight and roundabout transition paths are computed for a wide range of temperatures. Our study shows that the harmonic approximation for fluctuations about the steepest-descent paths is not valid even at relatively low temperatures and, furthermore, that factors related to entropy have to be determined by the global geometry of the potential-energy surface (rather than just the local curvatures alone) for complex reaction systems. It is reasonable to expect that this algorithm is also applicable to higher dimensional systems. |
| doi_str_mv | 10.1063/1.2013213 |
| format | Article |
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| language | eng |
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| source | MEDLINE; AIP Journals Complete; AIP Digital Archive |
| subjects | Algorithms Chemistry, Physical - methods Computer Simulation Diffusion Entropy Models, Chemical Models, Statistical Models, Theoretical Normal Distribution Temperature Thermodynamics |
| title | Efficient transition path sampling for systems with multiple reaction pathways |
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